US2386323A - Method for accelerating the alkaline de-esterification of pectin - Google Patents
Method for accelerating the alkaline de-esterification of pectin Download PDFInfo
- Publication number
- US2386323A US2386323A US526308A US52630844A US2386323A US 2386323 A US2386323 A US 2386323A US 526308 A US526308 A US 526308A US 52630844 A US52630844 A US 52630844A US 2386323 A US2386323 A US 2386323A
- Authority
- US
- United States
- Prior art keywords
- pectin
- alkaline
- salt
- esterification
- reaction mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000001814 pectin Substances 0.000 title description 17
- 235000010987 pectin Nutrition 0.000 title description 17
- 229920001277 pectin Polymers 0.000 title description 17
- 238000005886 esterification reaction Methods 0.000 title description 11
- 238000000034 method Methods 0.000 title description 4
- 235000002639 sodium chloride Nutrition 0.000 description 23
- 150000003839 salts Chemical class 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 6
- -1 cation chloride Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N 2,3,4,5-tetrahydroxypentanal Chemical compound OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229940040387 citrus pectin Drugs 0.000 description 2
- 239000009194 citrus pectin Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000017788 Cydonia oblonga Nutrition 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 238000007257 deesterification reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0045—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Galacturonans, e.g. methyl ester of (alpha-1,4)-linked D-galacturonic acid units, i.e. pectin, or hydrolysis product of methyl ester of alpha-1,4-linked D-galacturonic acid units, i.e. pectinic acid; Derivatives thereof
Definitions
- This application is made under the act of A further object is to facilitate the use of milder reaction conditions, particularly lower temperatures, in order to reduce undesirable degradation of the reaction products.
- the rate of alkaline deesterification of pectin is substantially accelerated if a salt that yields cations in solution is added to the solution or suspension of pectin material either before or after it is adjusted to the pH at which de-esterification is to be carried out.
- a salt that yields cations in solution is added to the solution or suspension of pectin material either before or after it is adjusted to the pH at which de-esterification is to be carried out.
- the salts may be used. Common examples are sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, sodium acetate, ammonium acetate, and so forth.
- the rate of de-esterification in the presence of even low concentrations (less than 0.3 molar concentration) of monovalent cations is increased on the order of 2 times the rate obtained when no salt is added. Inthe presence of a divalent cation, the rate may be as great as five times that obtained in the absence of a salt.
- Example I cent de-esteriflcation was 80-85 minutes.
- Example II The procedure used in Example I was repeated except that 5.8 gms. of NaCl was added to the solution. The time required for 50 percent deesteriflcation was 40-45 minutes.
- Example III The procedure used in Example I was again repeatedexcept that 3.7 gms. of anhydrous CaClz was added to the solution. The time required for 50 percent de-esteriflcation was 18-20 minutes.
- Example IV A 0.5 percent solution of citrus pectin was maintained by continuous titration with alkali at pH 9.0 and 29.5 C. in the presence of a salt as indicated below. The corresponding rates are shown in the following table.
- salts composed of a variety of cations and anions cause an acceleration of the rate of alkaline de-esterification of pectin the selection of the best salt to use in any instance will depend on the particular conditions of reaction, on considerations of economy, and on the isolation procedure to be used. If the isolation procedure involves the use of organic solvents, it may be desirable to use a salt, such as ammonium acetate, that is relatively soluble in organic solvents in order to facilitate the preparation of low ash pectin. n the other hand, where the ash content is not so important, or where ashproducing isolationprocedures can be used, the use of other salts may be preferable.
- the accelerating effect of a salt on the rate of de-esteriflcation occurs throughout the range of alkaline pH values.
- the percent acceleration caused by the salt appears to be essentially independent of the pH. Likewise, it appears to be independent or the reaction temperature.
- the accelerant 'efiect occurs in any alkali which may be used for the de-esteriflcation of pectin.
- This invention is not limited to any particular pectin material. Purified and unpurified pectin from citrus fruit, apples, sugar beets, carrots, pea hulls, quinces, grapes, and so forth, may
- the step which comprises adding an ionizable salt selected from the group consisting of alkali metal, alkaline earth metal and ammonia salts to the reaction mixture.
- the step which comprises supplementing the reaction mixture with an ionizable salt selected from the group consisting of alkali metal, alkaline earth metal, and ammonia salts which will yield cations in the reaction mixture.
- the step which comprises supplementing the reaction mixture with an ionizable suliate which will yield alkali metal cations in the reaction mixture.
- the step which comprises supplementing the reaction mixture with an ionizable acetate which will yield ammonium cations in the reaction mixture.
- the step which comprises adding an ionizable salt of an alkali metal to the reaction mixture.
- the step which comprises adding an ionlzable salt of an alkaline earth metal to the reaction mixture.
- the step which comprises adding an ionizable ammonia salt to the reaction mixture.
- the step which comprises supplementing the reaction mixture with an ionizable chloride which will yield alkaline earth metal cations in the reaction mixture.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
Patented Oct. 9, 1945 UNITED srATas PATENT OFFICE METHOD FOR ACCMERATING THE W- LINE DE-ESTERIFICATION F PECTIN Hans Llneweaver and Rolland M. McOi-eady,
. Berkeley, Calii., assignors to oi America as the United States represented by Claude, lit. Wickard, Secretary of Agriculture, and his successors No Drawing. Application March 13, 1944, Serial No. 526,308
8 Claims. (c1. ace-e095) '(Granted'under the act or March amended April 30, 1928; 370 0.
This application is made under the act of A further object is to facilitate the use of milder reaction conditions, particularly lower temperatures, in order to reduce undesirable degradation of the reaction products.
We have found that the rate of alkaline deesterification of pectin is substantially accelerated if a salt that yields cations in solution is added to the solution or suspension of pectin material either before or after it is adjusted to the pH at which de-esterification is to be carried out. It will be apparent that a wide variety of the salts may be used. Common examples are sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, sodium acetate, ammonium acetate, and so forth. The rate of de-esterification in the presence of even low concentrations (less than 0.3 molar concentration) of monovalent cations is increased on the order of 2 times the rate obtained when no salt is added. Inthe presence of a divalent cation, the rate may be as great as five times that obtained in the absence of a salt.
Our invention is illustrated by the following examples:
Example I cent de-esteriflcation was 80-85 minutes.
Example II The procedure used in Example I was repeated except that 5.8 gms. of NaCl was added to the solution. The time required for 50 percent deesteriflcation was 40-45 minutes.
3, 1883, as G. 757) Ewmple III The procedure used in Example I was again repeatedexcept that 3.7 gms. of anhydrous CaClz was added to the solution. The time required for 50 percent de-esteriflcation was 18-20 minutes.
Example IV A 0.5 percent solution of citrus pectin was maintained by continuous titration with alkali at pH 9.0 and 29.5 C. in the presence of a salt as indicated below. The corresponding rates are shown in the following table.
Relative rate Concentra- S I of dc-esterifia t cation Mala per liter Percent Ewample V- A 2 percent solution of citrus pectin was de'- esterified in 0.33 N NHtOH at 15 C. (pH 10.7 to 10.9) in the presence of a salt as indicated below.
The corresponding relative rates determined by Relative rate Salt figfi of de-esterification M ols per liter Percent The examples given above show that the acceleration of the rate of de-esterification effected by the added salt is attributable to the cations, since in the presence of a. divalent cation chloride at half (or less) the molar concentration, the acceleration is greater than is the case with a monovalent cation chloride. Thus it appears that the rate of acceleration is independent of the chloride ion. However, while the higher valent cations affect a greater acceleration at equal concentrations or at equal ionic strengths,
55 special precautions may have to be taken when they are used to avoid the mechanical difliculties all beused.
2 incident to gel formation. As shown by the examples, the influence or the salt on the rate of de-esterification tends to level of! near 0.1 to 0.2 molar concentration.
Since salts composed of a variety of cations and anions cause an acceleration of the rate of alkaline de-esterification of pectin, the selection of the best salt to use in any instance will depend on the particular conditions of reaction, on considerations of economy, and on the isolation procedure to be used. If the isolation procedure involves the use of organic solvents, it may be desirable to use a salt, such as ammonium acetate, that is relatively soluble in organic solvents in order to facilitate the preparation of low ash pectin. n the other hand, where the ash content is not so important, or where ashproducing isolationprocedures can be used, the use of other salts may be preferable.
The accelerating effect of a salt on the rate of de-esteriflcation occurs throughout the range of alkaline pH values. The percent acceleration caused by the salt appears to be essentially independent of the pH. Likewise, it appears to be independent or the reaction temperature. Also, the accelerant 'efiect occurs in any alkali which may be used for the de-esteriflcation of pectin.
It is evident that at any given temperature and pH, a considerable saving in the time required for de-esterflcation of pectin can be effected by the addition of a salt tothe reaction mixture. By the addition of salt, it is also possible to carry out the de-esteriflcation under milder conditions without increasing the reaction period, which makes it possible to use lower reaction temperatures and lower pH values efliciently, and thus minimize degradation due to changes other than demethoxylation.
This invention is not limited to any particular pectin material. Purified and unpurified pectin from citrus fruit, apples, sugar beets, carrots, pea hulls, quinces, grapes, and so forth, may
Having thus described our invention, we claim:
1. In the alkaline de-esteriilcation of pectin materials, the step which comprises adding an ionizable salt selected from the group consisting of alkali metal, alkaline earth metal and ammonia salts to the reaction mixture.
'2. In the alkaline de-esterification of pectin materials, the step which comprises supplementing the reaction mixture with an ionizable salt selected from the group consisting of alkali metal, alkaline earth metal, and ammonia salts which will yield cations in the reaction mixture.
3. In the alkaline de-esterification of pectin materials, the step which comprises supplementing the reaction mixture with an ionizable suliate which will yield alkali metal cations in the reaction mixture.
4. In the alkaline de-esteriflcation of pectin materials, the step which comprises supplementing the reaction mixture with an ionizable acetate which will yield ammonium cations in the reaction mixture.
5. In the alkaline de-esterification of pectin materials, the step which comprises adding an ionizable salt of an alkali metal to the reaction mixture.
6. In the alkaline de-esteriflcation of pectin materials, the step which comprises adding an ionlzable salt of an alkaline earth metal to the reaction mixture.
7. In the alkaline de-esteriflcation of pectin materials, the step which comprises adding an ionizable ammonia salt to the reaction mixture.
8. In the alkaline de-esteriflcation of pectin materials, the step which comprises supplementing the reaction mixture with an ionizable chloride which will yield alkaline earth metal cations in the reaction mixture.
HANS LINEWEAVER. ROLLAND ML MCCREADY.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US526308A US2386323A (en) | 1944-03-13 | 1944-03-13 | Method for accelerating the alkaline de-esterification of pectin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US526308A US2386323A (en) | 1944-03-13 | 1944-03-13 | Method for accelerating the alkaline de-esterification of pectin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2386323A true US2386323A (en) | 1945-10-09 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US526308A Expired - Lifetime US2386323A (en) | 1944-03-13 | 1944-03-13 | Method for accelerating the alkaline de-esterification of pectin |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2386323A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2496306A (en) * | 1946-08-09 | 1950-02-07 | Harry S Owens | Isolation of low-methoxyl pectins |
| US20070031572A1 (en) * | 2003-07-07 | 2007-02-08 | Kmc Kartoffelmelcentralen Amba | Method for preparing fibre-containing pectin and products and uses thereof |
-
1944
- 1944-03-13 US US526308A patent/US2386323A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2496306A (en) * | 1946-08-09 | 1950-02-07 | Harry S Owens | Isolation of low-methoxyl pectins |
| US20070031572A1 (en) * | 2003-07-07 | 2007-02-08 | Kmc Kartoffelmelcentralen Amba | Method for preparing fibre-containing pectin and products and uses thereof |
| US7833558B2 (en) | 2003-07-07 | 2010-11-16 | Kmc Kartoffelmelcentralen Amba | Method for preparing fibre-containing pectin and products and uses thereof |
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